Benzimidazole compositions and methods of use



United States Patent 3,506,767 BENZIMIDAZOLE COMPOSITIONS AND METHODS OFUSE Wilhelm Ernst Frick, Basel-Land, Anton G. Weiss, Basel,

and Thomas Wenger and Walter Traber, Riehen, Switzerland, assignors toGeigy Chemical Corporation, Ardsley, N.Y., a corporation of New York NoDrawing. Filed Aug. 4, 1966, Ser. No. 570,159 Claims priority,application Switzerland, Aug. 6, 1965, 11,111/65; Nov. 11, 1965,15,586/65; Jan. 5, 1966,

Int. Cl. A01n 9/12, 9/14, 9/22 U.S. Cl. 424-273 6 Claims ABSTRACT OF THEDISCLOSURE The present invention relates to a new process for theproduction of 1,2-nitranilines, 1,2-phenylene diamines, benzimidazoles,particularly 2-halogeno or 2-halogeno alkyl-substituted benzimidazoles;to compounds obtained by this process, compositions containingbenzimidazoles, and to process for the protection of organic material,particularly keratin-containing material, by treatment with such activesubstances.

For the production of aryloxy-l,Z-phenylenediamines, up to the presentonly the synthesis of 3-phenoxy-1,2- phenylene-diamine described by M.Oesterlin (Monatshefte 57, 31-44 (1953)) has been known. This processprogresses by more than 5 steps to the difiiculty identifiable endproduct. The second amino group is obtained by reduction of asubsequently introduced nitro group into the aminodiphenyl ether. H. A.Scarborough (Soc. 132, 236 l- 2367 (1929)) describes the care necessaryand difficulties encountered in the nitration. Halogenations of nitro-,aminoand acetamido-diphenyl ethers are also known from this publication;these however, only lead in each case to the monohalogen compound or totar products. Phenoxy-l,2-nitranilines or 1,2-phenylenediamines whichare monoor poly-halogenated have not been described up to the present.

It is also known that aromatic nitro compounds react on heating witharomatic primary amines in an alkaline medium to form azoxy and azocompounds,

Surprisingly, it has now been found that good yields of aryloxy andarylthio 1,2-nitranilines and, from these, the corresponding1,2-phenylenediamines are obtained in a very pure state when a metalsalt of an optionally nonionogenically further substituted monoorpoly-nuclear phenol or thiophenol is reacted with a 3- or 5- halogen-2-nitroaniline which can contain other non-ionogenic, inert substituentsand, if desired, the nitro group in the aryloxyorarylthio-2-intro-aniline is reduced to the amino group.

A particular embodiment of the present invention con- 3,506,767 PatentedApr. 14, 1970 cerns the production of 1,2-nitrani1ines and of1,2-phenylenediamines of the general Formula I In this formula:

one of the symbols Y and Y represents the nitro group or the primaryamino group, the other represents hydrogen or halogen,

Z and Z each represent hydrogen or halogen,

R represents lower alkyl, halogeno-lower alkyl, lower alkyl or loweralkylthio, halogen, particularly chlorine or bromine,

X represents oxygen or sulfur,

in represents an integer of from 0 to 5.

These compounds are obtained by reacting a compound of the generalFormula II lm wherein R, X, and m have the meanings given in Formula I,in the presence of a strong inorganic base, with ahalogen-Z-nitroaniline of the general Formula III I )v Z2 (III) wheneinone of the two Zs represents halogen, the other Z and Z and Y representhydrogen or halogen and p is 1 or 2 and if desired, reducing the nitrogroup in the condensation product to the amino group.

The preferred temperatures for the condensation lie within the range of100 to 200 C. It is of advantage to the progress of the reaction if theinorganic base is added as concentrated aqueous solution. The principalbases are the hydroxides of alkali and alkaline earth metals. Thecondensation can be accelerated by the addition of catalysts such ascopper.

The reduction of the intro group to the amino can be performed by theusual methods, eg, with catalytically activated hydrogen in the presenceof metal catalysts such as Raney nickel palladium etc, with nascenthydrogen by means of base metals and acids, with stannous salts in acidsolution etc. Preferably the reduction is performed by Bchamps method,i.e. with pulverised iron in weakly acid aqueous solution.

By the new process, the compounds of general Formula I are obtained inyields of -95% and in a state almost pure enough for analysis. Thus,laborious purification operations are not necessary. It is particularlysurprising that, for the reaction with the phenolates or mercaptides,the amino group of the halogen-Z-nitraniline has not to be protected byacylation. On the contrary, tests have shown that on using correspondinghalogen-nitro-N-acetyl anilines, the yield on saponification of theacetylamino group, drops to about 30%.

The compounds according to the invention are valuable intermediateproducts for the production of pharmaceuticals, pest control agents,optical brighteners and dyestuffs. For example, 1,2-phenylenediaminesare used for the production of blue fluorescentbis-benzimidazol-2-ylethylenes which, as valuable optical white shades,have become of industrial importance. On condensing1,2-phenylenediamines with 1,4,5,8-naphthalene tetracarboxylic acid,valuable vat dyest-uifs are obtained. 1,2-nitranilines are valuablediazo components for the production of ice dispersion and pigmentdyestufis.

According to a second aspect 'of the invention, the above-mentioned1,2-nitranilines and 1,2-phenylene diamines are preferably used asintermediates for the production of 2-halogeno benzimidazoles of theFormula IV wherein R is hydrogen, halogen, or trifluoromethyl;

Hal is halogen, preferably chlorine or bromine,

R is hydrogen or a metal cation,

X is oxygen, sulfur, sulfinyl, or sulfonyl,

Z is halogen, nitro, hydroxy, mercapto, alkyl or up to 6 carbon atoms,alkoxy of up to 6 carbon atoms, alkylthio of up to 6 carbon atoms,trifluoromethyl, lower alkyl-substituted amino, benzoylamino, halogenobenzoylamino, trifiuoromethyl benzoylamino, benzene sulfonylamino,halogenosulfonyl-amino, alkylsulfonylamino, alkylsulfinyl,alkylsulfonyl, trifluoromethyl benzenesulfonylamino, trifluoromethylhalogeno benzenesulfonylamino or the radical of sulfonic acid and itssalts, ester and amide forms,

m is an integer of from 1 to 5, and

p is an integer of from to 3.

These 2-halogeno benzimidazoles have excellent insecticidal andacaricidal activity, particularly however, marked activity againstinsects and their stages of development, such as moth larvae and alsofur and carpet beetle larvae, which injure keratin material. Due totheir affinity to keratin fibers, the 2-halogen-benzimidazolederivatives of general Formula I draw onto these fibers from aqueousdispersions and, if R is hydrogen, also from aqueous solutions of theirsalts, and, in this way, the keratin material treated therewith isprotected from injury caused by the larvae of clothes moths and othermoths as well as that caused by larvae of fur and carpet beetles(Anthrenus and Atta genus) These compounds are also active, however,against other inserts, including termites, as well as mites and are thusused for general pest control, particularly for industrial applicationin the protection of plants and, in particular, material, e.g. for theprotection of organic materials such as paper, wood, textiles, syntheticmaterials, etc. against attack by insects and mites.

The compounds with a halogenated phenoxy group, are of particularinterest.

The new Z-halogeno benzimidazoles are prepared according to theinvention, by reacting a 2-hydroxy-benzimidazole of the Formula V (z). NRm \C-OH 4 1278 (1961); J. Chem. Soc. 1963, 2934; Gazz. Ital. 88, 13(1958)). The production of 2-hydroxy benzimidazoles serving as startingmaterial by various usual processes is also described in thesecitations.

Alternatively, Z-mercaptO-benzimidazoles may be used as startingmaterial for the production of 2-halogeno benzimidazoles. The new2-halogeno benzimidazoles are then obtained by:

(a) oxidizing such starting materials with a suitable oxydizing agentsuch as potassium permanganate to form the corresponding 2-sulfonic acidderivative and reacting this with phosphorus pentachloride or phosphorusoxychloride to form the instable sulfonic acid chloride which decomposesinto the corresponding Z-chlorobenzimidazole (Annalen der Chemie 647, 57(1961) describe similar reactions), or

(b) treating such starting materials with chlorine in the presence ofwater and, if desired another solvent, and, if desired, transforming the2-halogen-benzimidazoles obtained according to (a) or (b) into theirsalts. (Similar reactions are described in J. Am. Chem. Soc. 72 4890(1950)). Carbon tetrachloride and, particularly, glacial acetic acid,are used, eg as solvents for this reaction.

When the oxidative chlorination of nuclear unsubstitutedZ-mercapto-benzimidazole is performed in acetic acid at room temperaturefor a longer time (5 hours) then, with simultaneous chlorination of thenucleus, a mixture of 2,5,6-trichloro-benzimidazole and2,5,6,7-tetrachlor-benzimidazole is formed (Knobloch and Rintelen,Archiv. der Pharmazie 291 (vol. 63) pages 180l84 (1958) TheZ-mercapto-benzimidazoles which can be used as starting materials in themodified process according to the invention, can be obtained by knownprocesses, e.g. by reacting correspondingly substitutedo-phenylenediamines with carbon disulfide, thiophosgene or thiourea. Theo-phenylenediamines necessary for these reactions can be produced intheir turn by the process of the present invention as described above.

If desired, phenylthio--1,2-phenylenediamines can be oxidized by knownmethods to obtain phenylsulfinylor phenylsulfonyl-1,2-phenylenediamines.

According to a third aspect, the present invention relates to new2-trifiuoromethyl benzimidazoles processes for their production andcompositions containing such 2- trifluoromethyl benzimidazoles.

2-trifluoromethyl-benzimidazoles which contain at least one phenylradical bound to the benzo ring by way of an oxygen or sulfur atom, thesulfinyl or sulfonyl group, have not been known up to the present. Ithas now been found that such compounds containing the substituentmentioned in the 4(7)- and/ or 5 (6)-position, in which the phenylradical itself is unsubstituted or can be substituted by ionogenic ornon-ionogenic groups, have excellent pesticidal properties and are thusvaluable for the control of pests of all types.

The Z-trifluoromethyl benzimidazoles of Formula VI wherein R representsa halogen atom having an atomic weight below 100, or a halogenoalkylradical,

R represents a halogen atom having an atomic weight below or a loweraliphatic hydrocarbon redical optionally bound by way of an oxygen orsulfur atom, the sulfinyl or sulfonyl group,

Z represents a halogen atom having an atomic weight below 100, hydrogen,lower alkyl, lower alkoxy, lower alkylmercapto;

R, represents hydrogen, or a metal cation;

X represents an oxygen or sulfur atom, the sulfinyl or sulfonyl group,and

m" represents an integer of 0 to 3,

n" represents an integer of 0 to 2,

p represents an integer from 1 to 3 and, if R =H, also there salts, areof particular importance for the combatting of pests because of theirexcellent insecticidal, acaricidal and microbicidal (bacteriostatic andfungistatic) properties. These compounds have an excellent action oninsects particularly on the larvae of insects which eat keratin fibers,e.g. Tineidae and Dermestidae, so that they are particularly suitablefor the protection of keratin material.

In general Formula VI of halogen atoms having an atomic weight below100, chlOrine and bromine atoms are preferred. The trifluoromethylradical is the preferred halogenoalkyl radical R By lower aliphatichydrocarbon radicals, alkyl or alkenyl radicals having straight orbranched chains are meant those, such as the methyl, ethyl, allyl ormethallyl radical, the propyl, butyl or amyl radicals. In the case of Rthese radicals can also be bound, by way of an oxygen or sulfur atom,the sulfonyl or sulfonyl group, to the phenyl radical.

The new 2-trifluoromethyl-benzimidazoles are produced according to theinvention by reacting a 1,2-phenylenediamine having at least one phenylradical bound by way of an oxygen or sulfur atom, the sulfinyl orsulfonyl group as substituent, with trifiuoroacetic acid and/or with oneof its reactive functional derivatives.

The following compounds are meant by functional derivatives oftrifiuoroacetic acid in the process according to the invention:trifiuoroacetic acid anhydride, trifiuoroacetic acid bromide andchloride, the esters, e.g. methyl, ethyl esters, as well as thecorresponding ortho esters and metal salts of trifiuoroacetic acid, alsotrifiuoroacetic acid amidine. The reaction can be performed simply withtrifluoroacetic acid alone or with one of the derivatives given above.It is preferred, however, that trifiuoroacetic acid be used in thereaction together with one of these derivatives, e.g. withtrifiuoroacetic acid anhydride.

New benzimidazoles from the group embraced by general Formula VI arepreferably produced by reacting a 1,2-phenylenediamine of the generalformula wherein R R Z, R X', m", n" and p have the meanings given inFormula VI, with trifiuoroacetic acid and trifiuoroacetic acid anhydrideand, optionally, in reaction products so obtained wherein R is hydrogen,converting them into the corresponding salts with an inorganic ororganic base.

To produce such salts of the new benzimidazoles, inorganic bases,particularly the hydroxides of alkali metals, or organic bases,particularly tertiary amines, are used. The water soluble salts are ofparticular importance as the application of the new active ingredientsis preferably made from aqueous media.

Benzimidazoles of general Formula VI wherein R is a lower aliphatichydrocarbon radical or a benzyl or phenethyl radical optionallysubstituted in the nucleus by halogen, can be obtained also frombenzimdazoles wherein R is hydrogen or from salts of such benzimidazolesby reaction with an alkylating or aralkylating agent, optionally in thepresence of an acid binding agent. Alkylating or aralkylating agents areesters of lower aliphatic or a'raliphatic alcohols with strong acidssuch as halogen hydracids, sulfuric acid or aryl sulfonic acids.Inorganic bases, e.g. the hydroxides and carbonates of alkali andalkaline earth metals or organic bases, particularly tertiary aminessuch as trialkylamines of pyridine are used as acid binding agents.

The 1,2-phenylenediamines used as starting materials for the processaccording to the invention can be produced from correspondingnitranilines by reduction according to Bchamps. These nitranilines canbe produced by condensation of metal salts of phenols and thiophenolswith halogen-nitranilines.

The condensation product with thiophenol, after acylation of the aminogroup, can then be oxidised to form the corresponding phenylsulfinyl orphenylsulfonyl acylnitranilines. Hydrogen peroxide, potassiumpermanganate or organic peracids such as peracetic acid are examples ofoxidizing agents.

The term lower alkyl as used per se or in combination with other groupsin the specification and appended claims means hydrocarbons with up to 6C-atoms like, for instance, methyl, ethyl, propyl, isopropyl, butyl etc.

The term lower alkoxy is used for an alkoxy group with up to 6 C-atomslike, methoxy, ethoxy, propoxy etc.

The following examples serve to illustrate the present invention withoutlimiting the same thereto. Where not otherwise stated, parts are givenas parts by weight. The temperatures are given in degrees Centigrade.

EXAMPLE 1 (a) 48.2 parts of 3,4,6-trichloro-2-nitraniline are added to18.82 parts of melted phenol at 90 and the whole is heated to 130. Atthis temperature, 11.2 parts of aqueous 50% potassium hydroxide solutionare added dropwise within 1 hour. The water is continuously distilledfrom the mixture. The reaction mixture is then heated for 6 hours at140150 while stirring whereupon it is cooled to 100 and 300 parts byvolume of boiling water are added. The solution is then stirred for 3hours and afterwards left to stand for 12 hours. 1500 parts by volume ofwater are then added to the reaction mixture, then 50 parts by volume of30% aqueous sodium hydroxide solution are added and finally it isstirred for 2 hours. The precipitate formed is filtered off undersuction, washed several times with water and dried in vacuo over NaOH.(Yield of crude product 65 parts=93.2% of the theoretical. M.P. 113115).After recrystallisation from ethanol,4,6-dichloro-3-phenoxy-2-nitraniline melts at 133135. The yield of pureproduct is 41.5 parts (69.4% of the theoretical).

(b) 14 parts by volume of acetic acid are added to 66 parts of ironpowder in 350 parts by volume of water at 80 and the mixture is heatedfor 15 minutes at 100. At the same temperature, 59.8 parts of4,6-dichlor0-3-phenoxy-2-nitraniline are added in portions within 1 hourand the mixture is refluxed for 16 hours. After cooling to about 80, thereaction is made weakly phenolphthalein alkaline with 20 parts of sodiumcarbonate and 400 parts by volume of chlorobenzene are added. Afterbringing quickly to the boil it is filtered hot and the residue iswashed with hot chlorobenzene. The chlorobenzene phase is separated in aseparating funnel, washed with water, dried over sodium sulphate andevaporated to dryness in vacuo. The 4,6-dichloro-3-phenoxy-1,2-phenylenediamine is obtained as an oil in the crude state and isobtained in crystalline form from hot benzene/petroleum ether. The yieldof pure product is 39.4 parts. MJP. 85-87".

EXAMPLE 2 (a) 48.2 parts of 3,5,6-trichloro-2-nitraniline are added to29.4 parts of melted 4-chlorothiophenol at and the whole is heated to11.2 parts of aqueous 50% potassium hydroxide solution are then addeddropwise to the melt within 1 hour. The amount of water added isdistilled off within 5 hours at a temperature of 130- The melt is thenstirred for another 4 hours at 145, then cooled to 100 and 200 parts byvolume of hot water are added. The mixture is then left to stand for 12hours at room temperature. 1000 parts by volume of water and 50 parts byvolume of 30% aqueous sodium hydroxide solution are then added and thewhole is stirred for 2 hours at room temperature. The crystallineprecipitate is isolated, washed several times with water and dried intheair. Yield of crude product: 65 parts (93.2% of the theoretical),M.P. 113-115". Recrystallised from ethanol, 4,6dichloro-3-(4'-chlorophenylthio)-2-nitraniline melts at 119-120". Theyield of pure product is 49.5 parts=7l% of the theoretical.

(b) 14 parts by volume of 80% acetic acid are added to 66 parts of ironpowder in 350 parts by volume of water and the mixture is heated for 15minutes at 90-100". 69.8 parts of 4,6 dichloro 3(4'-chlorophenylthio)-2- nitraniline are then added in portions within 2hours at the same temperature and the reaction mixture is refluxed for18 hours. The reaction is carefully made phenolphthalein alkaline with18 parts of sodium carbonate, the reaction mixture is cooled to 80 and,at this temperature, 400 parts by volume of chlorobenzene are added.After stirring for a short time, it is filtered hot. The residue iswashed with a little hot chlorobenzene. The chlorobenzene phase isseparated in a separating funnel, washed with water, dried over sodiumsulphate and then evaporated to dryness under water jet vacuum. Theyield Of crude 4,6-dichloro-3-(4'-chlorophenylthio)-1,2-phenylenediamine is 62 parts; M.P. 116-118" (sinters at 110). Recrystallisedfrom benzene, the product melts at 116- 117 (yield: 48.2 parts=75.5% ofthe theoretical).

From equivalent amounts of correspondingly substituted nitranilines andphenols or thiophenols, the phenoxy or phenylthio-2-nitranilines givenin the first column are obtained and reduced to the 2-phenylenediaminesgiven in column 2 by the processes described in Examples 1 and 2.

4, G-dichloro-S-(4-chlorophenoxy)- 4, 6-dichl0ro-3-(4-chloropheuoxy)-Z-nitraniline, M.P. 127-129. 1, 2-phenylenediamine, M.P.

phenoxy) -1, 2-phenylene- 4, 6-diehloro-3-(2, 4 41101110)- diamine, M.P.105-107". 4, 6-dichloro-3(2, ll-dichlorophenoxy)-2-nitraniline, M.P.134-135. 4, 6-dichloro-3phenylthio-2- phenoxy) -1, 2-phenylenediamiuo,

.P. 115-117. 4, -dichloro-3-phenylthio-l, 2- nitraniline, M.P. 157159.4, 6-dichloro-3-2, 5-dicl1lorophenylenediamine, oil. 4, 6-dichl0ro-3-(2,5-dichlorophenylthio) -2-nitraniline, M .l? i65-1 phenylthio)-1,2-phenylene- 67. diamine, M.P. KEG-168 3, dichloro-5-(4-ehlor0-phenoxy)-Z-nitraniline M.P. 190-192.

3, 4-dichloro-5-(4 -chloropl1enoxy)- 1, 2-phenylenediamine, Ml. 104-106.

The following o-phenylene diamines are produced in the same way asdescribed in the foregoing examples:

Table I 12) 3,5-dichloro-6-phenoxy-l,2-phenylenediamine M.P. -87 C.

( 13) 3,5-dichloro-6-phenylthio-1,2-phenylendiamine0il (l4)3,5-dichloro-6-(4-chlorophenoxy -1,2-phenylene-' diamineM.P. 116-117 C.

(15) 3 ,5 -dichloro-6- 2,4'-dichlorophenoxy) 1 ,2-pheny1- endiamineM.P.-117 C.

(16) 3 ,5 -dichloro-6- 3 ,4-dichlorophenoxy)-1,2-phenylenediamineM.P.105-107 C.

(17) 3,5-dichloro-6-(2,3'-dichlorophenylthio)-1,2-

phenylenediamine-M.P. 166-168 C.

( 18) 3 ,5 -dichloro-6- (4'-bromophenoxy) 1 ,2-phenylenediamineM.P.82-84 C.

( l9) 3,5-dichloro-6-(4-methoxyphenoxy) -1,2-phenylenediamineoil 20) 3,5 -dichloro-6-( 2',4',5 '-trichlorophenoxy) -1,2-

phenylenediamine-MP. 143-145 C.

(213,5-dichloro-6-(3-trifluoromethyl-4-chlorophenoxy)-1,2-phenylenediamineM.P.117-120 C.

(22) 3,5-dichloro-5- (4'-chlorophenoxy) -1,2-phenylenediamineM.P.188-190 C.

(23) 3,5-dichloro-5-(2,4'-dichlorophenoxy)-1,2-phenylenediamine-crudeoil (24) 3,5-dichloro-5-phenylthio-1,2phenylenediamine oil (25)3,5-dichloro-5- 3,4'-dichlorophenoxy) -1,2phenylenediamine-oil (26)3,5-dichloro-5-(2,5 -dichlorophenylthio)-1,2-

phenylenediamine-MP. 184-186 C.

(27) 3 ,5 -dichloro-4- 4'-chloro phenoxy 1 ,2-phenylenediamineM.P.l43-144 C.

(28) 3,5-dichloro-4-(2,4'-dichlorophenoxy) -1,2-phenylenediamine-oil(29) 3-bromo-4- (4'-chloro henoxy) -5-chloro-1,2-phenylenediamineM.P. 156-1 57.5 C.

(30) 4-chloro-5-(4'-chlorophenylsulfinyl) -1,2-phenylenediamine (314-chloro-5-(4-chlorophenylsulfonyl) -1,2-phenylenediamineM.P. l69-172 C.

(32) 3,5-dichloro-6- (4-chlorophenylsulfinyl) -1,2-

phenylenediamine-MP. 190-192 C.

(3 3) 3 ,5 -dichloro-6-(4'-chlorophenylsulfonyl) -1,2-

phenylenediamine-M.P. 140-142 C.

EXAMPLE 3 15.2 parts of 2 mercapto4,6-dichloro-7-(3',4'-dichlorophenoxy)-benzimidazole (produced bycondensation of 3,5 dichloro 6 (3',4'-dichlorophenoxy)-1,2-phenylenediamine with CS CSC1 or thiourea) are dissolved in 400 parts byvolume of glacial acetic acid to which 35 parts by volume ofconcentrated hydrochloric acid and 2 drops of concentrated HNO areadded. At 20-25", a solution of 11.2 parts of chlorine in 200 parts byvolume of carbon tetrachloride are added dropwise within 1 hour and theWhole is stirred for 14 hours at 20. The reaction mixture is thenevaporated to dryness and made strongly alkaline with concentrated NaOHpH 11-12) whereupon the product almost completely dissolves. Undissolvedparticles are filtered off and the pH of the filtrate is adjusted to pH4 with concentrated hydrochloric acid whereupon the productprecipitates. The precipitate is filtered off under suction washed anddried at 60. The pure2,4,6-trichloro-7-(3'4'-dichlorophenoxy)-benzimidazole melts at 116122.

EXAMPLE 4 12 parts of 4,6 dichloro-7-(3' trifluoromethyl 4- chlorophenoxy) 2 hydroxy-benzimidazole (produced by a condensation of 3,5dichloro-6-(3trifiuoromethyl 4' chlorophenoxy) 1,2-phenylenediarninewith phosgene, urea or chlorocarbonic acid ester) in 120 parts by volumeof phosphorus oxychloride are boiled until a clear solution is formed. Aweak stream of hydrogen chloride is then introduced for 3 hours. Afterthis time, the reaction mixture is cooled and the excess phosphorusoxychloride is distilled off in vacuo. The oily residue is poured into1000 parts of 20 cold water, and, after stirring for 1 hour, isextracted with ether. The ether phase is washed until it is neutral,dried with sodium sulphate and evaporated. Recrystallised from toluene,the pure 2,4,6trichloro 7 (3'trifiuoromethyl-4'-chlorophenoxy)-benzimidazole obtained melts at234-235 EXAMPLE 5 7.7 parts of 2,4,6-trichloro 7 (3,4dichlorophenoxy)-benzimidazole are dissolved in 80 parts by volume ofdimethyl formamide and, after the addition of some parts per thousand ofSeCl chlorine gas is added. The temperature is kept at 2530. Afterintroducing chlorine gas for 2 hours, the reaction mixture is pouredinto 500 parts of ice water and the precipitated resinous product isisolated and dissolved in 15 parts by volume of 30% NaOH with theaddition of 1000 parts of water. The somewhat opaque solution isfiltered and precipitated with concentrated hydrochloric acid.Recrystallisation from ethanol/water yields pure 2,4,5,6 tetrachloro- 7(3',4' dichlorophenoxy) benzimidazole which melts at 245-247.

EXAMPLE 6 7.7 parts of 2 mercapto-4,6 dichloro 7-phenoxybenzirnidazoleare suspended in, 150 parts by volume of concentrated hydrobromic acid(40%) and then, at room temperature, a solution of 16 parts of brominein 50 parts by volume of hydrobromic acid is added dropwise. The wholeis then stirred for 24 hours at 35-40. The reaction mixture is thenpoured into 1000 parts by volume of ice Water, the product whichprecipitates is filtered ofi? and washed with water. The residue isdissolved in 1 N sodium hydroxide solution, active charcoal is added,the solution is filtered and the residue is precipitated by acidifyingwith concentrated hydrobromic acid to pH 2-3. The resulting2,5-dibromo-4,6-dichloro- 7-phenoxy-benzimidazole is filtered oif,washed until it is neutral and dried.

EXAMPLE 7 (l) 2-nitro-3-amino-4,4,6-trichloro diphenylether 56.7 g. of 2nitro 3,4,6-trichloroacetanilide (German Patent 178,299) are heatedtogether with 25.7 g. of pchlorophenol and 44.8 g. of caustic potashsolution (50%) in an oil bath at 150-160 C. for 16 hours while stirring.Volatile portions are distilled off thereby. After cooling to 100, theobtained melt is poured into a mixture of 2 1. water and 200 ml. 1 NNaOH. The mixture is stirred at 25 for 30 minutes and the productfiltered off by suction. The crude material is re-crystallized fromalcohol. The yield is 20.7 g. (corresponding to 31.2% of the theoreticalyield). The obtained 2-nitro-3-amino-4,4', 6-trichloro diphenylethermelts at 125-127 C.

(2) 2,3-diamino-4,4,6-trichlorodiphenylether 120 ml. of water are heatedand 19.8 g. of iron powder added. The mixture is heated to 90 C. Whilestirring. 4.5 ml. of glacial acetic acid are added and the mixturestirred for another 10 minutes at 90 to 95 C. During the next hour, 20g. of 2-nitro-3-amino 4,4,6 trichlorodiphenylether are added graduallyand subsequently 25 ml. of alcohol. Stirring is continued throughout thenight while boiling under reflux. After cooling down the mixture, solidsodium carbonate is added until the mixture is alkaline tophenolphthalein. After the addition of 180 ml. of chloro benzene, themixture is heated to boiling and the insoluble parts are filtered offthrough a china clay filter while still hot. The organic phase isseparated from the aqueous phase by means of a separating funnel. Theorganic phase is then washed with water and dried over sodium sulfate.The obtained chloro benzene solution is evaporated to dryness and theobtained product recrystallized from alcohol. 15.6 g. of 2,3-

diamino 4,4,6-trichlorodiphenylether are obtained having a melting pointof 97 to 99 C.

(3 2-mercapto-4,6-dichloro-7- [4'-chlorophenoxy] benzimidazole 15.2 g.of 2,3diamino-4,4,6-trichloro diphenylether and 70 ml. of alcohol areplaced in a flask and a solution of 10 g. of potassium ethylxanthogenate in 15 ml. of water is added. The mixture is heated toboiling under reflux for 40 hours While stirring. While still hot, ml.of water are added and the mixture adjusted to a pH of 6 'by theaddition of glacial acetic acid. After cooling, the precipitate isfiltered off by suction and washed with water. The crude product isdissolved in a mixture of 30 ml. concentrated NaOH, 30 ml. alcohol, and650 ml. water. Insoluble material is removed by filtration, and thefiltrate acidified by the addition of hyrochloric acid. The obtainedprecipitate is filtered 01f by suction, washed thoroughly with water anddried. 9.2 g. of Z-mercapto- 4,6 dichloro 7[4'-chlorophenoxy]benzimidazole are obtained having a melting point of245 to 247 C.

(4) 2,4,6-trichloro-7-[4'-chlorophenoxy]benzimidazole 9.2 g. of 2mercapto 4,6 dichloro-7-[4'-chlorophenoxy]benzimidazole are dissolved in250 ml. of glacial acetic acid with warming and 25 ml. of concentratedhydrochloric acid as well as 2 drops of concentrated nitric acid areadded. The mixture is cooled to 17 C. and chlorine passed in (up to atotal of 6 g.) during One hour while stirring. Stirring is continued foranother 15 minutes. The reaction mixture is poured into 1 l. of iceWater, the precipitate is filtered off by suction and washed with water.The product is recrystallized from alcohol, then from benzene. 2.5 g. of2,4,6-trichloro-7-[4'-chlorophenoxy1benzimidazole are obtained having amelting point of l12l20 C.

The following compounds according to the invention may be produced inthe manners described in Examples 3 to 7.

Table II (1 )42,6-dichloro-5-phenoxy-benzimidazole-M.P. 240- (2 2,6-dichloro-S-phenylmercapto-benzimidazole-M.P.

(3 2,6-dichloro-5- (4-chlorophenoxy -benzimidazole- M.P. 199-201 C.

(4) 2,6-dichloro-5-(4'-chlorophenylmercapto)-benzimidazole-M.P. 207-208C.

(5 2,6-dichloro-5-(4-bromophenoxy) -benzimidazole M.P. 193-195 C.

(6) 2,6-dichloro-5- 2,4-dichlorophenoxy -benzimidazoleM.P. 216-218 C.

(7) 2,6-dichloro-5-( 3',4-dichlorophenoxy)-benzimidazoleM.P. 220-227 C.

(8) 2,6,7-trichloro-5- 4'-chlorophenoxy) -benzirnidazoleM.P. 245 C.

(9) 2,6,7-trichloro-S-(4-chlorophenylmercapto -benzimidazole-M.P.273-275 C.

(10) 2,6,7-trichloro-5- 2',5 -dichlorophenyl-mercapto benzimidazoleM.P.23 7-239 C.

(1 1) 2,6-dichloro-5-(4'-methoxyphenoxy)-benzimidazoleM.P. 201-203 C.

( 12) 2,4,6-trichloro-7-phenoxy-benzimidazole-MP.

( 13) 2,4,6-trichloro-7-phenylmercapto-benzimidazole M.P. 197-205 C.

( 14) 2,4,6-trichloro-7- 4'-chlorophenoxy) -benzimidazoleM.P. 112-120 C.

(15) 2,4,6-trichloro-7- 4-chlorophenylmercapto -benzimidazole-M.P.2l3216 C.

( 16) 2,4,6-trichloro-7- 4-br0mophenoxy) -benzimidazole-M.P. 127-13 0 C.

( l7) 2,4,6-trichloro-7- 2',4-dichlorophenoxy -benzimidazoleM.P. 117 C.

1 Decomposition.

(18) 2,4,6-trichloro-7- (2,5 '-dichlorophenyl-mercapto benzimidazoleM.P.197200 C.

( 19) 2,4,6-trichloro-7-(2,4,5'-trichlorophenoxy)-benzimidazoleM.P. 145C.

(20) 2,4,6-trichloro-7-(4'-methoxyphenoxy)-benzimidazoleM.P. 164166 C.

(21 2,4,6-trichloro-7-( 4'-chlorophenylsulfinyl -benzimidazole-M.P.292295 C.

(22) 2,4,6-trichloro-7-(4'-chlorophenylsulfonyl)-benzirnidazole--M.P.271-273 C.

(23) 2,4,6,7-tetrachloro-5-(4chlorophenoxy)-benzimidazole-M.P. 285296 C.

(24) 2,4,5,6-tetrachloro-7-(4-chloropl1enylsulfinyl)- benzimidazoleM.P.310312 C.

(25) 2,4,6-trichloro-5-bromo-7- 3 ',4'-dichlorophenoxy benzimidazoleM.P.263-264 C.

( 26) 2,6-dichloro-4,7-dibromo-5- (4-chlorophenoxy benzimidazole-M.P.285-287 C.

(27) 2,4,6,7-tetrachloro-5-(2,4'-dichlorophenoxy) -benzimidazole (28)2,6-dichloro-4,7-dibromo-5-(2',4'-dichlorophenoxy) -benzimidazole (29)2,4,6-trichloro-5-(4'-chlorophenoxy)-benzimidazole (30)2,4,6-trichloro-5- (4'-chlorophenylmercapto -benzimidazole (31)2,4,6-trichloro-5-(2',4'-dichlorophenoxy)-benz1m1dazole (32)2,4,6-trichloro-5-(2',5-dichlorophenylmercapto)- benzimidazole (33)2,4,6-trichloro-5-(4'-chloro-5-trifiuoromethylphenoxy -benzimidazole(34) 2,4,6-trichloro-5- 2,4,5 '-trichlorophenoxy -benzimidazole (3 5)2,6-dichloro-4-bromo-5- (4-chlorophenoxy) -benzimidazole 36)2,6-dichloro-4-bromo-5-(4'-chlorophenylmercapto) benzimidazole (37)2-chloro-5-phenylsulfamoyl-benzimidazoleM.P.

(3 8 2,4,6-trichloro-5- (4'-chlorophenylsulfamoyl -benzimidazole--M.P.223-225 C.

(39) 2,4,6-trichloro-5- 3 -trifiuoromethyl-4-chlorophenylsulfamoyl) -benzimidazole (40)2,4,6-trichloro-5-(N-methyl-N-3,4-dichlorophenylsulfamoyl)-benzimidazoleM.P.210 C.

(41 2-chloro-5- (tetrachloro-phenylsulfamoyl) -benzimidazole-M.P. 228229C.

(42) 2-chloro-5-(4'-chlorophenylsulfonylamino)-benzimidazole-M.P. 226227C.

(43)2-chloro-5-(2-methyl-4',5'dichloro-phenylsulfonylamino)-benzimidazoleM.P.236-237 C.

(44) 2,6-dichloro-5-methylsulfonylamino-benzimidazole (452,6-dichloro-5- (4'-chlorophenylsulfonyl -benzimidazole (46)2,4,6-trichloro-S-methylsulfonylamino-benzimidazole (47)2,4,6-trichloro-5- 4-chloro-phenylsulfonylamino benzimidazoleM.P. 190 C.

(48) 2-chloro-4,6,7-tetrabromo-5-methylsulfony1aminobenzimidazole (49)2-chloro-5-(3'-trifluoromethyl-4-chlorophenylsulfonylamino)-benzimidazoleM.P.188-l91 C.

(50)2,4,6,7-tetrachloro-5-(4-chlorophenyl-sulfonylamino)-benzimidazoleM.P.135 C.

(51) 2-chloro-5-( 3,4'-dichlorobenzoylamino)-benzimidazoleM.P. 214-215"C.

( 5 2) 2-chloro-5- 2',4',5 -trichlorobenzoylamino -benzirnidazoleM.P. 1283 C.

( 5 3) 2,4-dichloro-5-( 3 ',4'-dichlorobenzoylamino -benzimidazole (54)2,6-dichloro-5-(2,4,5'-trichlorobenzoylamino)- benzimidazole (55)Mixture of 70% 2,4,6,7-tetrachloro and 30% 2,4,6-

1 Decomposition.

-12 trichloro-S- 3,4'-dichlorobenzoylamino -benzimidazoleM.P. 170 C.(56)2-chloro-5-(3-trifluoromethyl-4'-chloro-phenylcarbamoyl)-benzimidazoleM.P.140 C.

The compounds of Formula IV which are illustrated by Examples 3 to 6 canbe used according to the usual methods for textile finishing. They haveaifinity to keratin material and are excellently suitable, therefore,for the protection of such materials from injury by insects, inparticular they are suitable for the wash and light fast moth-proofingof such materials both in the crude as well as in the processed state,for example of raw or processed sheeps wool as well as other animalhairs, fells and furs. In addition to the wash and light fastmoth-proofing in the dyebath, the compounds can also be used for theimpregnation of wool and woollen articles in dry cleaning processes, thematerials then becoming equally excellently moth proofed.

In addition to their insecticidal action on the larvae of the clothesmoth, the compounds of Formula IV are also active against the larvae ofthe fur and carpet beetles. The textiles treated in any way desired withthe compounds according to the invention such as woollen blankets,woollen carpets, woollen underwear, woollen clothes and knitted goods,are given protracted protection from the usual types of insects whichare injurious to keratin material.

The agents used for the protection of keratin materials against injuryby insects should contain the active substances of Formula IV in afinely distributed form. Thus, solutions, suspensions and emulsions ofthe active substances in particular are used.

The compounds containing a hydrogen atom in the heterocyclic ring (R=H), in the form of their alkali metal salts generally have good watersolubility. They can be applied to the keratin material direct fromthese aqueous solutions, either by dipping the material for a shorter orlonger time in the alkali metal salt solution, or spraying them with thesolutions, or by treating them in the solutions at a raised temperatureas in dyeing processes.

Because of their solubility in organic solvents, these compounds arealso particularly well suited for application from non-aqueous media.Thus, the materials to be protected can simply be impregnated with thesesolutions or, if a suitable solvent is chosen, the moth proof finishingcan be combined with a dry cleaning process.

Propylene glycol, methoxyethanol, ethoxyethanol and dimethyl formamidehave proved to be particularly suitable organic solvents, to which canbe added distributing agents and/or other auxiliaries such as soaps andaqueous sodium hydroxyde solutions. Emulsifying agents such as sulfatedricinus oil, sulfite waste liquor and fatty alcohol sulfates areparticularly mentioned as distributing agents.

EXAMPLE 8 First, a 20% solution of2,4,6-trichloro-7-(3',4-dichlorophenoxy)-benzimidazole in glycolmonomethyl ether is produced. 10 parts by volume of this solution arediluted with 200 parts by volume of a solvent suitable for dry cleaning,e.g. a suitable benzine fraction (Diluan S). If desired, other cleansingadditives can be added. The woollen articles are then treated in thiscleansing liquor in the usual way and subsequently centrifuged to acontent of solvent of about of the weight of the wool. After drying,they prove to be mothproofed.

Baths of the same or analogous composition can also be used in ananalogous way for the moth proofing of untreated or already otherwisetreated or cleaned articles.

Similar mixtures can also be used for the spraying of wool in everystage of processing.

The insecticidal action of Z-halogen-benzimidazole derivatives accordingto the invention of general Formula IV against inserts which injurekeratin material was tested as given below, and the textile materialscontaining keratin which had been treated with these active substanceswere tested as to resistance to attack by insects which injure keratinmaterial in the following way:

Test Methods and Results.-A 0.5% stock solution of each active substanceto be tested in ethylene glycol monomethyl ether (methyl Cellosolve) isprepared. Then an aqueous application liquor is prepared at roomtemperature which contains 20' ml. of the stock solution mentioned (0.1g. of active substance) in 400 ml. liquor. 10 g. of wool flannel arethen well wetted with hot water and introduced into the liquor at roomtemperature. While constantly circulating the woollen sample, the bathtemperature is raised to 60 C. within 15 minutes, then 2% of 80% formicacid (calculated on the weight of the wool) are added and the treatmentin the liquor is continued for another 30 minutes at this temperature.It is then cooled, the woollen sample is rinsed in running tap water,centrifuged and, for the purpose of drying, is hung up. Theconcentration of active substance is 1%, calculated on the weight of thewool.

The sample so dried is then subjected to the moth proofing test (injuryby clothes moth T ineola biselliella) according to the Swiss Associationfor Standardisation leaflet 95901 and also it is tested for fastness tothe fur bettle larvae (Attagenus piceus) and carpet beetle larvae(Anthrenus vo rax) according to Swiss Association for Standardisationleaflet 95902; the method for Anthrenus larvae was simply applied toAttagenus piceus larvae in that 6-7 week old larvae of the latter typewere used for the test. Basically, the method consists in cutting fourequal sized pieces from the treated wool flannel sample and exposingeach of these pieces for 14 days at a constant temperature (28 C.) andconstant relative humidity (65% to the attack (appetite) of 15 larvae ofthe relative pest (two pieces of material with the same pest).

The results are tabulated as follows:

Percent devoured material xxxx-Very good protection 5 xxx-Goodprotection 5-15 xxModerate protection 15-50 x-Insufl'icient protection50 Compound used in the test Moths Attagenus Anthrenus 2,6-dichloro-5-(4 -ehlorophenylmercapto)-benzlmidazole XXXX XX XXX 2,6-dichloro-5-(2, 4-diehlorophenoxy)-benzimidazole XXXX XX XXX 2,6dichloro-5-(3, 4-dichlorophenoxy)-benzimidazole XXXX XX XXX 2, 4,6-triehloro-5-(4-chloro phenoxy)-benzimidazole -1 XXX XXX XXX 2, 4,6-trichl0ro-7-phenoxybenzimidazole XXXX XXX XXX 2, 4,6-trichloroJ-phenylmercaptobenzimidazole -1 XXXX XXX XXX 2, 5-dibr0mo-4,6-dichloro-7- phenoxy-benzimidazole X XXXX XXX 2, 4,6-trichl0ro-7-(4-chlorophenoxy)-benzimidazole XXXX XXXX XXX 2, 4,6-trichloro-7-(4-chlorophenylmercapto)-benzimidazole XXXX XXXX XXX 2, 4,fi-trichlro-7-(2, '-dich1orophenylmercapto)-benzimldazole XXXX XXXX XXX2, 4, 6-trichl0ro-7-(2', 4-dichlorophenoxy)-benzimidazole XXXX XXXX XXX2, 4, 6-trichlor0-7-(3, 4'dich1orophenoxy)-benzimidazole XXXX XXXX XXX2, 4, 6-triehloro-5-br0m0-7-(3. 4-

dichlorophenoxy)-benizmidazole.. XXXX XXXX XXX 2, 4, 5,6-tetrachloro-7-(3, 4'-dichlorophenoxy)-benzimidazole XXXX XXXX XXX 2,4, 5, 6-tetrachl0ro-7-(4chlorophenylsulfinyl)-benzimidazole XXXX XXXXXXX 2, 6-dichloro-4, 7-dibromo-5-(4'- chlorophenoxy)benzimidazole XXXXXXXX XXX 2, 4, 6, 7-tetrachloro-5-(4-chlorophenoxy)-benzimidazole XXXXXXXX XXXX 2, 4, 6-trichl0ro-7-(2, 4, 5-trichlorophenoxy)-benzimidazoleXXXX XXXX XXX 2, 4, G-trichloro-7-(4-chl0ro-5-tribenzimidazole XXXX XXXXXXXX EXAMPLE 9 15 parts of 3-(3',4'-dichlorophenoxy)-4,6-dichloro-1,2-phenylenediamine are mixed at room temperature with 15 14 parts oftrifluoroacetic acid and 15 parts of trifluoroacetic acid anhydride andthe Whole is then refluxed for 2 hours. Excess trifluoroacetic acid andits anhydride are then distilled off in vacuo.

The residue is taken up in 4 N hydrochloric acid. The crystallineprecipitate obtained is filtered off and recrystallised from methanol.The 2-trifluoromethyl-4-(3,4-di chlorophenoxy)-5,7-dichlorobenzimidazoleobtained melts at Because of their good insecticidal, acaricidal andmicrobiocidal properties, the following 2-trifiuorornethylbenzimidazoles are particularly well suited for the combatting ofinsects, insect larvae, spiders and larval stages thereof,micro-organisms (bacteria and fungi) in plant protection, storesprotection and, in particular, for the protection of material:

M.P. 2-trifluoromethyl-4-(3,4-dichlorophenoxy)-5,7-

dichlorobenzimidazole 116-118 2-trifluoromethyl-4(4-chlorophenoxy)-5,7-dichloro-benzimidazole 205-207 2trifluoromethyl-4-(2'-dichlorophenoxy)-5,7-

dichloro-benzimidazole 194-196 2-trifluoromethyl-4-phenoxy5,7-dichlorobenzimidazole 204-206 2-trifluoromethyl-4-3-trifluoromethyl-4-chlorophenoxy) -5,7-dichloro-bcnzimidazole 199-201 2trifluoromethyl 4 phenylthio-5,7-dich1orobenzimidazole 177-1792-trifluoromethyl-4-(4'-chlorophenylthio)-5,7-dichloro-benzimidazole218-220 2 trifluoromethyl-4-(4-chlorophenylsulfinyl)-5,7-dichloro-benzimidazole 2-trifluoromethyl-4-(4' chlorophenylsulfonyD-5,7-dichloro-benzimidazole 238-240 2trifluoromethyl-4-(4'-chlorophenoxy)-5,7-dichloro-6-bromo-benzimidazoleZ-trifluorornethyl 4 (3,4-dichlorophenoxy)-5,6,7-trichloro-benzimidazole 2trifluoromethyl-4-(4-bromophenoxy)-5,7-dichloro-benzimidazole 201-2032-trifluoromethyl-4-(4-bromophenoxy) 5,7-dichloro-6-bromo-benzimidazoleZ-trifluoromethyl 6-(3',4-dichlorophenoxy)-5- chloro-benzimidazole 2trifluoromethyl 6-(4'-chlorophenylthio)-5- chloro-benzimidazole2-trifluoromethyl-6-(4-chlorophenylsulfinyl) 5- chloro-benzimidazole2-trifluoromethyl-6 (4'-chlorophenylsulfonyl)- 5,7-chloro-benzimidazole2 trifluoromethyl 6-(3,4'-dichlorophenoxy)-4,5,7-trichloro-benzimidazole 2-trifluoromethyl-6-(4'-chlorophenylthio)4,7-

dibromo-benzimidazole 2-trifluoromethy1-6 (4 chlorophenylsulfinyl)4,7-dibromo-5-chloro-benzimidazole 2trifluoromethyl-6-(4'-chlorophenylsulfonyl)4,7-dibromo-5-chloro-benzimidazole 2-trifluoromethyl-6 (4' bromophenoxy)5- chloro-benzimidazole 2 trifluoromethyl 6 (4-bromophenoxy)-5-chloro-benzimidazole2-trifluoromethyl-6-(3-trifluoromethyl-4-chlorophenoxy)-5-ch1orobenzimidazole 2-trifluoromethyl-4-(3,4-dichlorophenoxy)-5,7-

dichloro-6-methyl-benzimidazole 2-trifluoromethyl-4 (4' chlorophenoxy)5- fluoro-benzimidazole 2trifluoromethyl-4-(3-chlorophenoxy)-5,7-dichloro-benzimidazole -192 2trifluoromethyl-4-(2',5' dichlorophenylthio)- 5,7-dichloro-benzimidazole198-200 2-trifluoromethyl-4- 3 '-trifluoromethylphenoxy5,7dichloro-benzimidazole 177-179 2trifluoromethyl-4-(4'-ch1oro-3-trifluoromethyl-phenylthio)-5,7-dichloro-benzimidazole175-177 Z-trifluoromethyl 5 phenylthio-6-chloro-benzimidazole 222-2242-trifluoromethyl-5(3-trifluoromethyl-4-chlorophenoxy)-6-chloro-benzimidazole 263-2652-trifiuoromethyl-5-phenoxy-6-chloro-benzimidazole 205-2072-trifluoromethyl 4-(4'methoxyphenoxy)-5,7

dichloro-benzimidazole 186-188 2 trifiuoromethyl 4(2',4',5-trichlorophenoxy)-5.7-dichloro-benzimidazole 150-152 2trifiuoromethyl 5-(3',4'-dichlorophenoxy) 6-chloro-benzimidazole 238-240Z-trifluoromethyl-S (3 '-trifiuoromethyl-4-chlorophenylthio)-6-chloro-benzimidazole 208-210 2 trifluoromethyl5-(4'-chloropheny1thio)-6- chloro-benzimidazole 212-214 2trifluoromethyl-S-(2',4',5-trichlorophenoxy)- 6-chloro-benzimidazole225-227 2-trifluoromethyl-5 (2',5' dichloro phenylthio-6-chloro-benzimidazole 182-184 2 trifiuoromethyl 5 (4-chlorophenoxy)-6chloro-benzirnidazole 191-193 2-trifluoromethyl-5-(4'-methoxy phenoxy)6- chloro-benzimidazole 178-180 2 trifiuoromethyl5-(3'-trifluoromethyl-phenoxy)-6-chloro-benzimidazole 191-193Z-trifiuroromethyl 5 (4 bromophenoxy)-6- chloro-benzimidazole 196-198 2trifluoromethyl 4-(3',4-dichloro-phenoxy)- 5,6,7-trichloro-benzimidazole1 140 2-trifluoromethyl-4-(3 trifluoromethyl-4'-chloro-phenylsulfonyl)5,6,7-trichloro-benzimidazole 254-256 1 Decomposition.

Tests of the action of the new compounds on insects and spiders showedthat these active substances are good to very good contact and stomachpoisons and, at the same time they have a marked systemic action. A fewbenzimidazoles of the general Formula VI have good herbicidal propertiesand can thus also be used for influencing plant growth.

It has been found that the compounds of the general Formula VI haveexcellent protracted action on insects of the families Muscidae,Stomoxidae and Culicidae, e.g. the polyvalent resistent and normallysensitive house flies (Musca domestica), stable flies (Stomoxyscalcitrans) and mosquitoes (e.g. Adedes aegyptii, Culex fatigans,Anopheles stephensi), on insects of the families Curculionidae,Bruchidae, Dermestidae, Tenebrionidae and Chrysomelidae, e.g. granaryweevils (Sitophilus granaria), bean beetles (Bruchidius obtectus),larder beetles (Dermestes vulpinus), yellow meal worms (Tenebriomolitor), Colorado potato beetles (Leptinotarsus decemlineata) and theirstages of development, on the Pyralididae family, e.g. Mediterraneanflour moths (Ephestz'a kdhniella), the Blattidae family, e.g. Germancockroaches (Phyllodrom ia germanica) the Aphididae family, e.g. beanaphids (A phis fabae) and the Pseudococcidae family, e.g. citrusmealybugs (Planococcus citri). Tests on bean aphids (Aphis fabae) anddesert locusts (Schistocerca gregaria) indicate that the substances havean excellent systemic action. They have also a good action againsttermites. The active substances of general FormulaVI can be used asinsecticides for plant protection, protection of stores and for theprotection of organic materials of all types. In addition, the activesubstances have a good action against the larval and adult stages ofspiders, e.g. the Tetranychidae family.

As has already been said, the new benzimidazoles of general Formula VIhave an excellent insecticidal action against insects which destroy byeating, particularly against the larvae of insects which eat keratinfibres such as moth larvae, other small butterflies, fur and carpetbeetles. The afiinity of the active substances to the keratin fibres isexcellent so that they are most suitable for the protection of crudeand'processed keratin material such as Wool and other animal hair, wooltextiles of all types, fells and furs, from injury by such insects. Agood insecticidal protection is given to the treated materials by theactive substances.

The insecticidal activity of Z-trifluorornethylbenzimidazoles isdetermined according to the same test as described in the foregoingparagraphs. The test results are given as follows:

Compounds 2-trifiuoromethyl-4-phenoxy-5, 7-

dichlorobenzimidazole Z-trifln oromethyl-l- (2 ,4 -d ichlorophenoxy)-5,7-dichlor0- bonzimidazole 2-trifluoromethyl-4-phenylthio-5, 7-

dichloro-b enzirnidazole 2-trifluoromethy1-4-(4-chlor0phenylthio) -5,7-dichloro-benzimidazole. 2-trifluoromothy1-4-(4-chlorophenoxy) -5,7-dichloi'o-benzimidazole Z-trifluoromethyl-4-(3'-chlorophenoxy) -5,7-dichloro-benzimidazole 2-trifluoromethyl-4-(4-chloro-3-triflnoromethyl) -5, 7 -dichlorobenzimidazole 2-trifluoromethyl-4-(2,5'-dichlorophenylmercapto-5, 7-diohlorobenzimidazole2-trifluoromethyl-4-(4-br0rnophenoxy) -5, 7-dichloro-benzimidazole2-trifluoromethyl-5-(phenylmercapto) -6-chloro-benzin1idazoleZ-tritluoromethyl-t-(3-trifluoromethyl-phenoxy) -5, 7-dichlorobenzimidazole 2-trifluoromethyl--[4-chloro-3- trifluoromethyl)-phenyl-thio]- 5, 7-dichlorobenzimidazole2-trifluoromethyl-5-(3-trifluoromethyl-t-chloro-phenoxy) -6-chlorobenzimidazole 2-trifluoromethyl-5-phenoxy-6- chloro-benzimidazole2-trifluoromethyl-4-(4-methoxyphenoxy) -5, 7-dichloroben zimidazole2-trifiuorornethyl-4-(2, 4, 5-trichlorophenoxy) -5, 7 -diohloro- MothsAttagenus Antln'enus In the agar incorporation test Worked out byLeonard and Blackford (testing of bacteria and fungi on agar into whichthe active substances have been incorporated in various concentrations),the new benzimidazoles show an excellent prohibition of growth ofmicro-organisms such asbacteria, e.g. gram positive and gram negativebacteria, and fungi, e.g. Aspergillus niger, lPem'cillium ita'licumFulmriwm oxysporum, Candida albicwns, Acrostalagmus spec. etc., so thatthey are particularly suitable for the protection of organic materialsof all types from destruction and damage by bacteria and fungi. Keratinmaterials such as skins, leather, wool, as well as materials based oncellulose such as wood, cellulose, paper, cotton, also preparations suchas pastes, printing thickeners made from starch and cellulosederivatives, oils of all types, treatment liquors for paper andtextiles, plastics and synthetic materials of all types etc. are givennot only insecticidal but also microbicidal protection by treatment withthe new active substances.

The active substances to be used according to the invention can be usedalone or combined with other known active substances. They can becombined, e.g. with halogenated salicylic acid alkylamides andalkylanilides, with halogenated diphenyl ureas, with halogenatedphenoxydiphenyl ureas, with halogenated benzoxazoles or benzoxazclones,with 2-chloromethylsulphonylamino polychlorodiphenyl ethers, withpolychlorohydroxydiphenyl methanes, with halogen dihydroxydiphenylsulphides, with halogen ated hydroxydiphenyl ethers, with bactericidal2-iminoimidazolidines or 2-imino-tetrahydropyrimidines or withbactericidal quaternary compounds or with certain dithiocarbamic acidderivatives such as with tetramethylthiuram disulfide. In admixture withsynergists and auxiliaries having a similar action such as succinic aciddibutyl ester, piperonyl butoxide, olive oil, peanut oil etc., theinsecticidal and acaricidal range of action of the active substancesmentioned is widened and their action is improved. Also, theinsecticidal action can be substantially improved; broadened and adaptedto given circumstances by the addition of other insecticides such asphosphoric, phosphonic, thiophosphoric or dithiophosphoric acid estersand amides, other carbamic acid esters, halogenated hydrocarbons, DDTanalogues, pyrethrins and synergists thereof.

The new active substances are applied in the form of solid or liquidagents such as, ducts, sprinkling agents, granulates, aqueousdispersions which are obtained from wettable powders, pastes or emulsionconcentrates, and also as solution or aerosol. For the protection oforganic materials, the active substances are brought into the mostfinely distributed form as dispersions or solutions of active substance.

The agents according to the invention are produced in the known way byintimately mixing the active substances with solid or liquid carriersand distributing agents. For the protection of material, particularlyorganic solvents have proved valuable such as: propylene glycol,methoxyethanol, ethoxyethanol and dimethyl formamide. As distributingagents, emulsifying agents, e.g. sulfated castor oil, sulfite wasteliquor and fatty alcohol sulfates can be used. The concentration ofactive substance in the agents is, e.g. 0.0 l80%. Also other biocidalactive substancesfor use in plant protection-also fertilisers and traceelements can be added to the agents according to the invention.

Keratin materials can be impregnated with the active substances by themost varied textile finishing processes such as hot or cold, aqueousdye, bleaching, chroming, pad dyeing or after-treatment baths. The newactive substances are fixed excellently onto the keratin fibre not onlyby hot application but also by cold application. Even after coldapplication, the new active substances have high grade wet fastnessproperties, e.g. fastness to washing and milling.

Because of the solubility inorganic solvents, the active substances arealso well suitable for application from nonaqueous media. Here, thematerials to be protected can simply be impregnated with the solution.With a suitable choice of solvent, the materials can be given aninsecticidal and microbicidal finish also in a dry cleaning process.

Forms of compositions are described in the following text in which theactive substances can be used in plant protection and for the protectionof keratin materials.

Dust

To produce a dust, 10 parts of 2-trifluoromethyl-4-phenoxy-5,7-dichlorobenzimidazole, 5 parts of highly dispersed silicicacid and 85 parts of talcum are intimately mixed. Such a dust can beused, e.g. for combatting German cockroaches and ants.

18 Wettable powder To produce (a) a 50% and (b) a 10% wettable powder,the following components are used:

The amounts of active substance mentioned are intimately mixed insuitable mixers with the additives and the mixture is milled incorresponding mills and drums. A wettable powder is obtained which canbe diluted With water to form suspensions of any concentration desired.Such suspensions are mainly used for combatting insects in plantprotection.

Emulsion concentrate To produce (a) a 50% and (b) a 25% emulsionconcentrate, the following components are mixed together:

(a) 50 parts of 2-trifluoromethyl-4-(3,4-dichlorophenoxy-5,7-dichloro-benzimidazole 17.5 parts of Z-methoxyethanol 22.5 parts ofxylene 8 parts of nonylphenol/polyglycol ether condensate 2 parts ofdodecyl benzene sulfonate calcium salt.

10 parts of 2-trifluoromethyl-4-(4-bromophenozy)-5,7-dichloro-benzimidazole 25 parts of diacetonyl alcohol 2 parts ofalkylaryl polyglycol ether 3 parts of a combination emulsifying agent(nonylphenolpolyoxyethylene-dodecyl benzene sulfonic acid calcium salt)60 parts of xylene.

These concentrates can be diluted with water to form emulsions of anyconcentration desired. Such emulsions are used, e.g. to combat insectsin plant protection and the protection of stores.

Paste To produce a 45% paste, the following substances are used:

45 parts of 2-trifluoromethyl-4-(4'-chlorophenylsulfonyl)-5,7-dichloro-benzimidazole,

5 parts of sodium aluminum silicate 14 parts of cetyl polyglycol ether(condensate from saturated C C fatty alcohols and 8 mols of ethyleneoxide) 1 part of oleyl polyglycol ether (oleyl alcohol+5 mols ofethylene oxide condensate) 2 parts of spindle oil 10 parts ofpolyethylene glycol ether (Carbowax) 23 parts of water.

The active substance and the additives are intimately mixed and milledin suitable apparatus. A paste is obtained from which, by dilution withwater, suspensions of any desired concentration can be produced.

Agents according to the invention for combatting insect larvae whichinjure keratin fibers and the use of these agents for the protection ofkeratin materials from injury by such pests are further illustrated inthe following examples. Parts are given therein as parts by weight andthe temperatures are given in degrees centigrade.

1 9 EXAMPLE I 0.5 part of 2-trifluoromethyl-4-(3',4'-dichlorophenoxy)-5',7-dichloro-benzimidazole, in the form of the sodium salt, aredissolved with the help of parts of 0.1 N sodium hydroxide solution anda little ethanol. This solution is diluted with 3000 parts of water and100 parts of wool are treated in this liquor for minutes at 60. 5 partsof 10% acetic acid are then added and the treatment is continued foranother hour at 60. The wool is then rinsed and dried in the usual way.It proves, on testing, to be resistent to attack by moth, fur beetle andcarpet beetle larvae.

EXAMPLE II First, a solution of2-trifluoromethyl-4-(3,4-dichlorophenoxy)-5,7-dichloro-benzimidazole inglycol monomethyl ether is produced. 10 parts by volume of this solutionare diluted with 200 parts by volume of a solvent suitable for drycleaning, e.g. a suitable benzine fraction (Diluan C). If desired,additives which promote cleansing can be added. The woolen articles arethen treated in the usual way in this cleaning liquor and thencentrifuged to a solvent content of about 100% of the weight of thewool. After drying, they prove to be mothproof.

In an analogous manner, the same baths or those of analogous compositioncan also be used for mothproofing untreated articles or articles whichhave already been treated in some way or cleaned.

Similar mixtures can also be used for sprinkling on or spraying wool inany stage of processing.

EXAMPLE III To apply 2-trifluoromethyl-4-(3',4'-diehlorophenoxy)-5,7-dichloro-benzimidazole, the following process, for example, can beused:

0.5 part of active substance are dissolved in 10 parts of dimethylformamide and the solution is poured into 3000 parts of water containingabout 1-2 parts of an emulsifying agent, e.g. sulfated castor oil.

100 parts of wool are treated in this liquor at the boiling temperaturefor 30 minutes. After rinsing and drying, the wool proves to bemothproof.

Naturally, other auxiliaries and also dyestuffs can be added to thetreatment baths in Examples I and H.

We claim:

1. A composition comprising from 0.01 to 80% by weight of abenzimidazole compound of the formula:

20 wherein R is chlorine, or bromine, or trifluoromethyl;

R is chlorine, bromine, lower alkyl, lower alkoxy,

lower alkylthio, sulfinyl or sulfonyl;

R is chlorine or bromine;

R is hydrogen or an alkali metal cation;

X is oxygen, sulfur, sulfinyl or sulfonyl;

m is an integer of from 0 to 3;

n is an integer of from 0 to 2;

p is an integer of from 1 to 3; and a carrier compatible with saidcompound.

2. A method for protecting keratin-containing material fromkeratin-devouring insects and their larvae by applying thereto aninsecticidally effective amount of the composition as defined in claim1.

3. A method for prohibiting the growth of bacteria by applying thereto abacteriocidally effective amount of the composition as defined in claim1.

4. A method for prohibiting the growth of fungi by applying thereto af-ungicidally effective amount of the composition as defined in claim 1.

5. A composition comprising from 0.01 to by weight of a benzimidazolecompound of the formula:

References Cited Chem. ABS., Jan. 3, 1966, vol. 64: 1015. Chem. ABS.,Oct. 11, 1965, vol. 63:9954. Chem. ABS., Mar. 28, 1966, vol. 64: 10335.

ALBERT T. MEYERS, Primary Examiner L. SCHENKMAN, Assistant Examiner US.Cl. X.R. 260309.2

Disclaimer 3,506,767 .-WiZheZ m Ernst Fm'clc, Basel-Land, Anton G.Weiss, Basel, Thomas WengeT and Walter T'mbe'r, Riehen, Switzerland.BENZIMID- AZOLE COMPOSITIONS AND METHODS OF USE. Patent dated Apr. 14,1970. Disclaimer filed Sept. 17, 1970, by the assignee, Gez'gy Ohemz'calCorporation. Hereby enters this disclaimer to claim 4 of said patent.

[Oflim'al Gazette J a-nuary 26, 1.971]

